CN101851459A - Water-based polypyrrole anticorrosive paint and preparation method thereof - Google Patents
Water-based polypyrrole anticorrosive paint and preparation method thereof Download PDFInfo
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- CN101851459A CN101851459A CN201010011449A CN201010011449A CN101851459A CN 101851459 A CN101851459 A CN 101851459A CN 201010011449 A CN201010011449 A CN 201010011449A CN 201010011449 A CN201010011449 A CN 201010011449A CN 101851459 A CN101851459 A CN 101851459A
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Abstract
The invention discloses a water-based polypyrrole anticorrosive paint, which is prepared from the following components: 70 to 90 parts of water-based epoxy latex, 0.5 to 1.5 parts of antifoaming agent, 0.5 to 4 parts of dispersing agent, 0.5 to 5 parts of curing agent, 9 to 18 parts of polypyrrole preservative, and 0.1 to 3 parts of distilled water. A preparation method comprises the following steps of: synthesizing the polypyrrole preservative from pyrrole, ludox, organic acid, oxidant and the like; and mixing the synthesized polypyrrole preservative, the water-based epoxy latex, an auxiliary agent and the like uniformly to obtain the water-based polypyrrole anticorrosive paint. The water-based polypyrrole anticorrosive paint has the advantages of high polypyrrole content, high anti-corrosion performance, no pollution and low cost, is suitable to be used for preventing corrosion of metals, such as steel and the like, and is the environmental-friendly paint.
Description
Technical field
The present invention relates to a kind of water-based polypyrrole anticorrosive paint and preparation method thereof.
Background technology
The loss that metallic corrosion causes to the mankind is surprising, put into practice verified, adopting coating that metal is carried out corrosion prevention is most economical, practicality and effective means, but protective system now commonly used contains a large amount of organic solvents, in construction process to environment cause bigger pollution, to healthy grave danger that causes of workman; Protective system commonly used simultaneously also is rich in zinc, has not only consumed a large amount of zinc resources, also environment is caused serious heavy metal contamination.Therefore water-based anticorrosive paint has become the research focus and one of main developing direction of metal anti-corrosive paint.
Conducting polymer (polypyrrole, polyaniline and Polythiophene and their derivative) as the corrosion protection coating of metal, has good preservative effect.Wherein, because polypyrrole is synthetic easily, cost is lower, heat and chemical stability height, be a kind of polymers anti-corrosive paint that has practical value most therefore.Though polypyrrole has good corrosion prevention performance, its machining property, all relatively poor with the consistency of resin has limited its use.Now polypyrrole mainly contains with the ordinary method of resin-bonded: 1. dissolution method: add in the resin with special solvent dissolving back, this method can cause environmental pollution, and execution conditions are abominable, and solvent costs an arm and a leg and makes cost sharp increase; 2. physical blending method: as ball milled, expend a large amount of energy and time, and its dispersiveness and poor stability in resin, finally influenced the performance of polypyrrole antiseptic property; 3. earlier dissolve polypyrrole in amine curing agent, compound with Resins, epoxy again, this method has the defective that can't overcome: polypyrrole content is low, can't reach the content with best preservative effect.
In sum, there are many weak points in the prior art, are badly in need of a kind of polypyrrole content height, cost is low, performance is good protective system.
Summary of the invention
At above-mentioned prior art, the invention provides a kind of water-based polypyrrole anticorrosive paint, its polypyrrole content height, antiseptic property is good, and is pollution-free and cost is low, and the preparation method of this coating also is provided.
The present invention is achieved by the following technical solutions:
A kind of water-based polypyrrole anticorrosive paint is to be made by following component: 70～90 parts of aqueous epoxy emulsions, 0.5～1.5 part of defoamer, 0.5～4 part of dispersion agent, 0.5～5 part in solidifying agent, 9～18 parts of polypyrrole sanitass, 0.1～3 part of distilled water.
Described aqueous epoxy emulsion is the rich chemical industry water-base epoxy E-44 difficult to understand in Shanxi.
Described defoamer is methyl-silicone oil or dimethyl silicone oil.
Described dispersion agent is any in Virahol, ethylene glycol and ether thereof or propylene glycol and the ether thereof.
Described solidifying agent is quadrol or diethylenetriamine.
Described water is deionized water.
A kind of preparation method of water-based polypyrrole anticorrosive paint is characterized in that: may further comprise the steps:
(1) preparation polypyrrole sanitas: in there-necked flask, add pyrroles, silicon sol, organic acid, wherein, pyrroles, silicon sol, organic acid mass ratio are: 1: (1～2): (0.6～1.2), add 200g distilled water again, fully stir, treat that each component mixes the back and dropwise add aqueous oxidizing agent solution in system, behind reaction 12～24h, with methyl alcohol and distilled water repetitive scrubbing to filtrate is colourless, product promptly obtains the polypyrrole sanitas being ground to behind 55～65 ℃ of following vacuum-drying 10～12h below the fineness 60 μ m;
(2) with aqueous epoxy emulsion and 4: 1 according to a certain percentage～10: 1 abundant mixings of polypyrrole sanitas, and add after various auxiliary agents mix, apply or be sprayed on, solidified under the room temperature 1～3 day through the metallic surface of oil removing, processing of rust removing.
Described organic acid is tosic acid or camphorsulfonic acid.
Described aqueous oxidizing agent solution is the aqueous solution of Potassium Persulphate or ammonium persulphate, and wherein, the mass ratio of oxygenant and water is 1: (4.5～5.5); Oxygenant and pyrroles's mass ratio is 1: 1.
Water-based polypyrrole anticorrosive paint preparation method of the present invention is simple, has solved the problem of polypyrrole workability difference, can be subjected to scratching the back at coating and make bare metal avoid corrosion by generating passive film, and matrix metal is shielded.Protective system is coated on the 45# steel plate that polishing, oil removal treatment are crossed, and the curing back adopts paraffin to carrying out edge sealing around the steel plate, to eliminate because of the inhomogeneous potential test error that causes of edge coating.As working electrode, saturated calomel electrode is a reference electrode with steel plate, and concentration is that 3% NaCI solution is corrosive medium, the equilibrium potential of test steel plate under the room temperature.The 45# steel plate balance open circuit potential of the 45# steel plate that applies this protective system when not applying improved 150mV at least, the highest 220mV that improves, and preservative effect is remarkable.This protective system do not add any organic solvent and heavy metal thereby to environment without any pollution, polypyrrole heat and chemical stability height simultaneously may not produce carcinogenic substance even can not resemble after the decomposition the polyaniline yet, are a kind of environment-friendly type coatings.
Embodiment
The present invention is further illustrated below in conjunction with embodiment:
A kind of water-based polypyrrole anticorrosive paint of embodiment 1 preparation, step is as follows:
(1) take by weighing 10 gram pyrroles, 15 gram silicon sol (Qingdao Haiyang chemical industry), 12 gram tosic acid add 200 gram water, stir; 10 gram ammonium persulphates are dissolved in 50 grams obtain aqueous oxidizing agent solution in the water, be added drop-wise to then in pyrroles's solution, be colourless with methyl alcohol and distilled water repetitive scrubbing to filtrate behind the reaction 24h in the ice-water bath, product obtains the polypyrrole sanitas below being ground to fineness 60 μ m behind 60 ℃ of following vacuum-drying 12h.
(2) with aqueous epoxy emulsion and polypyrrole sanitas the abundant mixing of ratio, and add after various auxiliary agents mix, apply or be sprayed on, solidified 2 days under the room temperature through the metallic surface of oil removing, processing of rust removing according to 9: 1.
A kind of water-based polypyrrole anticorrosive paint of embodiment 2 preparations, step is as follows:
(1) take by weighing 8 gram pyrroles, 15 gram silicon sol (Qingdao Haiyang chemical industry), 10 gram tosic acid add 200 gram water, stir; 8 gram ammonium persulphates are dissolved in 44 grams obtain aqueous oxidizing agent solution in the water, be added drop-wise to then in pyrroles's solution, be colourless with methyl alcohol and distilled water repetitive scrubbing to filtrate behind the reaction 24h in the ice-water bath, product obtains the polypyrrole sanitas below being ground to fineness 60 μ m behind 60 ℃ of following vacuum-drying 10 h.
(2) with aqueous epoxy emulsion and 8: 1 according to a certain percentage abundant mixings of polypyrrole sanitas, and add after various auxiliary agents mix, apply or be sprayed on, solidified 3 days under the room temperature through the metallic surface of oil removing, processing of rust removing.
A kind of water-based polypyrrole anticorrosive paint of embodiment 3 preparations, step is as follows:
(1) take by weighing 15 gram pyrroles, 15 gram silicon sol (Qingdao Haiyang chemical industry), 12 gram camphorsulfonic acids add 200 gram water, stir; 15 gram ammonium persulphates are dissolved in 70 grams obtain aqueous oxidizing agent solution in the water, be added drop-wise to then in pyrroles's solution, be colourless with methyl alcohol and distilled water repetitive scrubbing to filtrate behind the reaction 12h under the room temperature, product obtains the polypyrrole sanitas below being ground to fineness 60 μ m behind 65 ℃ of following vacuum-drying 10h.
(2) with aqueous epoxy emulsion and 5: 1 according to a certain percentage abundant mixings of polypyrrole sanitas, and add after various auxiliary agents mix, apply or be sprayed on, solidified 2 days under the room temperature through the metallic surface of oil removing, processing of rust removing.
A kind of water-based polypyrrole anticorrosive paint of embodiment 4 preparations, step is as follows:
(1) take by weighing 12 gram pyrroles, 20 gram silicon sol (Qingdao Haiyang chemical industry), 15 gram tosic acid add 200 gram water, stir; 12 gram Potassium Persulphates are dissolved in 60 grams obtain aqueous oxidizing agent solution in the water, be added drop-wise to then in pyrroles's solution, be colourless with methyl alcohol and distilled water repetitive scrubbing to filtrate behind the reaction 12h under the room temperature, product obtains the polypyrrole sanitas below being ground to fineness 60 μ m behind 60 ℃ of following vacuum-drying 10h.
(2) with aqueous epoxy emulsion and 4: 1 according to a certain percentage abundant mixings of polypyrrole sanitas, and add after various auxiliary agents mix, apply or be sprayed on, solidified 3 days under the room temperature through the metallic surface of oil removing, processing of rust removing.
A kind of water-based polypyrrole anticorrosive paint of embodiment 5 preparations, step is as follows:
(1) take by weighing 15 gram pyrroles, 20 gram silicon sol (Qingdao Haiyang chemical industry), 10 gram camphorsulfonic acids add 200 gram water, stir; 15 gram Potassium Persulphates are dissolved in 67 grams obtain aqueous oxidizing agent solution in the water, be added drop-wise to then in pyrroles's solution, be colourless with methyl alcohol and distilled water repetitive scrubbing to filtrate behind reaction 24 h under the room temperature, product obtains the polypyrrole sanitas below being ground to fineness 60 μ m behind 55 ℃ of following vacuum-drying 12h.
(2) with aqueous epoxy emulsion and 7: 1 according to a certain percentage abundant mixings of polypyrrole sanitas, and add after various auxiliary agents mix, apply or be sprayed on, solidified 2 days under the room temperature through the metallic surface of oil removing, processing of rust removing.
Claims (9)
1. a water-based polypyrrole anticorrosive paint is characterized in that: be to be made by following component: 70～90 parts of aqueous epoxy emulsions, 0.5～1.5 part of defoamer, 0.5～4 part of dispersion agent, 0.5～5 part in solidifying agent, 9～18 parts of polypyrrole sanitass, 0.1～3 part of distilled water.
2. a kind of water-based polypyrrole anticorrosive paint according to claim 1 is characterized in that: described aqueous epoxy emulsion is water-base epoxy E-44.
3. a kind of water-based polypyrrole anticorrosive paint according to claim 1 is characterized in that: described defoamer is methyl-silicone oil or dimethyl silicone oil.
4. a kind of water-based polypyrrole anticorrosive paint according to claim 1 is characterized in that: described dispersion agent is any in Virahol, ethylene glycol and ether thereof or propylene glycol and the ether thereof.
5. a kind of water-based polypyrrole anticorrosive paint according to claim 1 is characterized in that: described solidifying agent is quadrol or diethylenetriamine.
6. a kind of water-based polypyrrole anticorrosive paint according to claim 1 is characterized in that: described water is deionized water.
7. the preparation method of the described a kind of water-based polypyrrole anticorrosive paint of claim 1 is characterized in that: may further comprise the steps:
(1) preparation polypyrrole sanitas: in there-necked flask, add pyrroles, silicon sol, organic acid, wherein, pyrroles, silicon sol, organic acid mass ratio are: 1: (1～2): (0.6～1.2), add 200g distilled water again, fully stir, treat that each component mixes the back and dropwise add aqueous oxidizing agent solution in system, behind reaction 12～24h, with methyl alcohol and distilled water repetitive scrubbing to filtrate is colourless, product promptly obtains the polypyrrole sanitas being ground to behind 55～65 ℃ of following vacuum-drying 10～12h below the fineness 60 μ m;
(2) with aqueous epoxy emulsion and 4: 1 according to a certain percentage～10: 1 abundant mixings of polypyrrole sanitas, and add after various auxiliary agents mix, apply or be sprayed on, solidified under the room temperature 1～3 day through the metallic surface of oil removing, processing of rust removing.
8. the preparation method of a kind of water-based polypyrrole anticorrosive paint according to claim 7, it is characterized in that: described organic acid is tosic acid or camphorsulfonic acid.
9. the preparation method of a kind of water-based polypyrrole anticorrosive paint according to claim 7, it is characterized in that: described aqueous oxidizing agent solution is the aqueous solution of Potassium Persulphate or ammonium persulphate, wherein, the mass ratio of oxygenant and water is 1: (4.5～5.5); Oxygenant and pyrroles's mass ratio is 1: 1.
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| CN201010011449XA CN101851459B (en) | 2010-01-14 | 2010-01-14 | Water-based polypyrrole anticorrosive paint and preparation method thereof |
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| CN201010011449XA CN101851459B (en) | 2010-01-14 | 2010-01-14 | Water-based polypyrrole anticorrosive paint and preparation method thereof |
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| CN102321420A (en) * | 2011-07-11 | 2012-01-18 | 中国船舶重工集团公司第七二五研究所 | Preparation method of heteropoly acid modified polypyrrole anti-corrosive coating |
| WO2012067489A1 (en) * | 2010-11-15 | 2012-05-24 | Mimos Berhad | Composition of solvent casting solution comprising polypyrrole powder for use as a transducer in biochemical sensor applications |
| CN103725162A (en) * | 2013-12-31 | 2014-04-16 | 合肥华清方兴表面技术有限公司 | Polypyrrole-bisphenol A epoxy resin composite coating and preparation method thereof |
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| CN104962174A (en) * | 2015-07-12 | 2015-10-07 | 李福军 | Water-based anti-corrosion paint and preparing method of water-based anti-corrosion paint |
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| WO2012067489A1 (en) * | 2010-11-15 | 2012-05-24 | Mimos Berhad | Composition of solvent casting solution comprising polypyrrole powder for use as a transducer in biochemical sensor applications |
| US20140227530A1 (en) * | 2011-05-23 | 2014-08-14 | Axalta Coating Systems Ip Co., Llc | Anti-corrosion coatings |
| CN102321420A (en) * | 2011-07-11 | 2012-01-18 | 中国船舶重工集团公司第七二五研究所 | Preparation method of heteropoly acid modified polypyrrole anti-corrosive coating |
| CN103725162A (en) * | 2013-12-31 | 2014-04-16 | 合肥华清方兴表面技术有限公司 | Polypyrrole-bisphenol A epoxy resin composite coating and preparation method thereof |
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| CN104962174A (en) * | 2015-07-12 | 2015-10-07 | 李福军 | Water-based anti-corrosion paint and preparing method of water-based anti-corrosion paint |
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| CN109825036A (en) * | 2019-02-15 | 2019-05-31 | 安庆市虹泰新材料有限责任公司 | A kind of modified epoxy and preparation method thereof |
| CN114591671A (en) * | 2022-03-28 | 2022-06-07 | 福建师范大学 | Preparation method and application of polypyrrole @ ZIF-8 modified epoxy resin anticorrosive paint |
| CN114591671B (en) * | 2022-03-28 | 2023-09-12 | 福建师范大学 | Preparation method and application of polypyrrole@ZIF-8 modified epoxy resin anticorrosive paint |
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